Process for producing resists on animal fibers



Patented May 1, 1928.

UNITED STATES PATENT OFFICE.

MAIN, GERMANY, ASSIGNORS TO GRASSELLI DYESTUFF CORPORATION,

OF NEW YORK, E. Y., A CORPORATION OF DELAWARE.

PROCESS FOR PRODUCING RESISTS' ON ANIMAL FIBERS.

lilo Drawing. I Application filed February 12, 1926, Serial No. 87,957,

Two colored effects may be produced on union fabrics containing animal and vegetable fibers,-e. g., fabrics consisting of mixtures of wool and cotton, or of silk and cottom-by using tannin in combination with tartar emetic. and tartar emetic requires the use of two substances which produce a reciprocal effect on the animal fiber of the union fabric in such a manner that the tannin'is fixed on the fiber by means of the tartar emetic.

Now we have found that the resist action on the animal fibers of union fabrics, such as that produced by the combined action of tannin and tartar emetic. can be obtained by substituting for the said reserving means aromatic sulfonic acid compounds the aromatic residues of which are connected with any residues,- which may also be sulfonated,by bridging atoms in the form of bivalent metalloids. The expression aromatic residues also comprises partially hydrated aromatic compounds. As bridging atoms may serve oxygen or sulfuratoms The said sulfonic acids, advantageously in the form of their salts, are to be added to the neutral dye-bath after the animal fiber, e. g. (wool) of the union fabric has been selectively dyed with the acid dyestuf'f, and simultaneously with the dyestuff for selectively dyeing the vegetable fiber of said union fabric, without there being any necessity for taking special steps for the fixation on the animal fiber of the products dissolved in Water. This peculiar reserving property of the sulfonic acid-salts, which are simply dissolved in the dye-liquor in the absence of'any special means for the fixation, can scarcely be explained by the tan ning property which the free sulfonic acids mostly possess only in a slight degree or not at all. Indeed, as is known, eventhe sulfonic acids of the kind in question which possess a very good tanning property, such as the sulfonic acid from methylidene dicresylether do not precipitate in a neutralized form solutions of gelatine, nor are they capable of transforming hides into leather. The action of thefi various sulfonic acids of the above-mentioned classesas regards their The treatment with tannin sodium thiodinaphthylsulfonate,

and in Germany February 20, 1925.

resist effect is in no way equally strong. It varies largely but it is in many cases stronger than that of tannin and tartar emetic.

Among the named products those which are, for instance, obtained from hydrocarbon sulfonic acids by condensing them for instance with sulfur halide, have proved to be particularly suitable for the purpose in question; furthermore, sulfonic acids of methylidene dicresylether and homologues thereof: also, the products obtainable by a strong oxidation of resinous bodies from phenol and sulfur chloride or from sulfurized phenols, the alkali salts of which products possess more or less the property of not being precipitated by strong acids; finally, the sulfonic acids obtainable from benzvlchloride sulfonieacid and phenol alkali or alkali salts of phenolic resins.

The following examples serve to illustrate our invention:

Example 1.-100 kg. of a union fabric of wool and cotton are treated for one hour at the boil in a dyebathcontaining 2 kg. of naphthol yellowS E L, 10 kg. of crystallized Glaubers salt and 4 kg. of sulfuric acid.

dyed in said dyebath. The union fabric is then rinsed with water and-treated, at 609 0., in a fresh-dyebath containing 2 kg. of dianil pure blue P. H., 3 kg. of sodium thiodinaphthylsulfonate and 20 kg. of crystallized Glaubers salt. As .a result of the latter treatment the cotton fibers of the union fabric are selectively dyed, the wool fibers being reserved by the action of the The said sodium thiodinaphthylsulfonate is obtained by causing 250 kg. of naphthalene to react with 300 kg. of concentrated sulfuric acid and 103 kg. of sulfur dichloride in the heat and subsequently neutralizing. It has most probably the formula:

(occupied positions unknown) E sample 2.-100 kg. of a union fabric of -Only the wool fibers of the union fabrics are t wool' and cotton are treated for one hour at the boilin a dyebath containing 2 kg. of aminonaphthol red B, 10 kg. of or stallized Glaubers salt and 4 kg. of su furic acid. Only the wool fibers of the union fabric are dyed in said dyebath. The fabric, after rinsing, is then treated, at 5060 C., in a fresh dyebath containing 2 kg. of dianil green B B N, 20 kg. of Glaubers salt and 3 kg. of the sulfonic acid compound product obtained by the oxidation with sodium peroxide of the resinous condensation product of phenol and sulfur chloride. As aresult of the latter treatment the cotton fibers of the union fabric are selectively dyed, the wool fibers being reserved by the action of the sulfonic acid compound.

The said sulfonic acid compounds act also as resists on the silk fibers of union fabnoisO-orn-o acid, compounds, the aromatic residues of which are connected with any residues by bridging atoms in the form of bivalent metalloids.

2. Process of obtaining two-colored effects on union fabric containing anlmal and Ve etable fiberswvliich comprises treating the 5. Process ofobtaining two-colored effects on union fabric containing animal and vegetable fibers which comprises treating the union fabric in an acid dyebath containing a dyestufi adapted for dyeing animal fiber, rinsing the so-treated union fabric and CHI nolsOcm-o rics of slik and cotton, so that if the halfsilk material (i. e., union fabric of silk and cotton) is dyed with direct dyestuffs, the silk fiber thereof remains conslderably purer than if no resist is used. For union fabrics of silk'and cotton, the dyeing process may be carried out as follows:

(3.) 1kg. of a union fabric of silk and cotton is treated inan acid bath with g. of pon'ceau G, the cotton-fiber thereof is then dyed in .a fresh bath, at 5060 (1, with 20 g. of dianil green GN to which are added 200 g. of Glaubers salt and g. of the sodium salt of the acid product resulting from the condensation of the resin obtained from phenol and acetic aldeh de with benzylchloride sulfonic acid. aid acid product has, in the form of its free acid, most probably the formula:

1,0 o-cnr-Osom union fabric in an acid dyebath' containing a dyestuif adapted for dyeing animal fiber, rinsing the so-treated union fabric and treating the same in a" non-acid dyebath containing a dyestufl? adapted for dyeing vegetable fiber to which has been added an aromatic sulfonic acid compound the aromatic residue of which is connected with any residues by bridging atoms in the form of hi- Valent metalloids.

.3. Union fabric the animal fiber of which has been resisted with an aromatic sulfonic acid compound the aromatic nucleus of which is connected with any residue by bridging atoms in the metalloids.

4.- Process for producing resists on animal form of bivalent fibers against dyestuffs, which consists in treating the animal fibers'with a solution of an aromatic sulfonic acid compound having most probably the formula:

treating the same in a non-acid dyebath containing a dyestufl adapted fordyeing vege-j i table fiber to which has been added an arothe formula 'maticsulfonic acid having most probably @dfilif) fibei' of which acid compound having most probably the 6. Union fabric the animal i'fonic formula:

has been resisted with an aromatic $11 In testimony whereof, we aflix our signatures,

KARL DAIMLER.

CARL ERECH MULLER. HIJGU GARTNEH. 

